US4051189A - Cyclic ethers of phenolic compounds and polymers thereof - Google Patents
Cyclic ethers of phenolic compounds and polymers thereof Download PDFInfo
- Publication number
- US4051189A US4051189A US05/711,651 US71165176A US4051189A US 4051189 A US4051189 A US 4051189A US 71165176 A US71165176 A US 71165176A US 4051189 A US4051189 A US 4051189A
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- ether
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- Expired - Lifetime
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- 229920000642 polymer Polymers 0.000 title claims abstract description 11
- 150000004292 cyclic ethers Chemical class 0.000 title abstract description 7
- 150000002989 phenols Chemical class 0.000 title 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 4
- 239000000460 chlorine Substances 0.000 claims abstract description 4
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 4
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 4
- 239000011737 fluorine Substances 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 5
- 229910015844 BCl3 Inorganic materials 0.000 claims description 3
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 claims description 3
- 239000012442 inert solvent Substances 0.000 claims description 2
- 239000002685 polymerization catalyst Substances 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims 2
- 101150108015 STR6 gene Proteins 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 7
- 238000000465 moulding Methods 0.000 abstract description 2
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 abstract 1
- 150000001491 aromatic compounds Chemical class 0.000 abstract 1
- 125000003118 aryl group Chemical group 0.000 abstract 1
- 101150035983 str1 gene Proteins 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 8
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 5
- ACGUYXCXAPNIKK-UHFFFAOYSA-N hexachlorophene Chemical compound OC1=C(Cl)C=C(Cl)C(Cl)=C1CC1=C(O)C(Cl)=CC(Cl)=C1Cl ACGUYXCXAPNIKK-UHFFFAOYSA-N 0.000 description 5
- 229960004068 hexachlorophene Drugs 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229930185605 Bisphenol Natural products 0.000 description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- -1 alkylidene compound Chemical class 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000001640 fractional crystallisation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000002195 soluble material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D321/00—Heterocyclic compounds containing rings having two oxygen atoms as the only ring hetero atoms, not provided for by groups C07D317/00 - C07D319/00
- C07D321/12—Eight-membered rings
Definitions
- the present invention relates to new cyclic ethers or ortho bisphenol and are produced by reacting a molar excess of orthobisphenol with bifunctional alkylene or alkylidene compound. It would be expected that such reaction would yield polymeric ethers, however, the products of the reaction are found to be a simple monomeric cyclic ether.
- the process is a condensation process and is carried out using an alkali metal or alkali metal hydroxide as a reactant, for example, sodium, potassium, or their hydroxide.
- the amount of alkali metal hydroxide used is generally between about 180 and 240 mole percent of the bisphenol utilized. Although additional amounts of alkali metal hydroxide may be used, the reaction is not proportionally speeded and additional subsequent removal problems will be encountered.
- the use of less than about 180% alkali metal hydroxide is operative, at a slower rate, however, the present process is not a rapid one and slowing the reaction does not appear to be advantageous.
- the ethers of the present invention may be characterized by the following formula: ##STR2## wherein R is independently selected from the group of hydrogen, chlorine, bromine and fluorine.
- the bifunctional alkylene or alkylidene compound utilized as a reactant is suitably a dihalogen derivative such as dibromomethane or dichloromethane.
- the reaction is effected by the formation of the corresponding alkali metal halide together with the ether product.
- the reaction may conveniently be carried out at atmospheric pressure and reflux temperatures. Under these conditions the time required for the reaction to go to completion varies with the reactants and their concentration, but may be as long as eight days. Such reaction may be illustrated: ##STR3##
- the halogenated compounds of the present invention have the added attribute of fire-retardant properties and are also useful as fire-retardant additives in plastic compositions.
- the cyclic methyl ether of hexachlorophene: ##STR4## is found to have strong bactericidal power, similar to hexachlorophene.
- the methylene ether is soluble in various liquids which are poor solvents for hexachlorophene and are useful in the preparation of new bactericidal mixtures.
- the cyclic ethers of the present invention may be easily polymerized using known techniques by reaction in the presence of a polymerization catalyst if either the R in the ortho or para positions of the phenol groups is hydrogen.
- the R in the ortho position is hydrogen.
- Catalysts found most effective are BF 3 , BCl 3 and PF 5 .
- a catalyst range of from 0.5 to 25% by weight of the methylene ether has been found useful.
- the polymerization reaction is carried out in an inert solvent such as hexane.
- the ether is initially mixed with the solvent, air removed, and the catalyst added. The reaction is suitably carried out at ambient temperature and pressure.
- the polymer products of the present invention may be characterized by the following formula: ##STR5## wherein R is independently selected from the group consisting of hydrogen, chlorine, bromine and fluorine and n is at least 5 and averages between about 30 and about 300.
- the crude product was recrystallized from a 50/50 mixture of ethanol and water. It melted at 107°-109° C and had the following analysis: C 79.28%; H 5.11%; MW 214; calculated for the cyclic methylene ether: C 79.2%; H 5.7%; MW 212.
- the NMR and IR spectra showed that the cyclic structure had been formed.
- Example 5 The BF 3 of Example 5 was replaced by BCl 3 . Polymer was recovered by evaporation of the solvent. Its infrared and NMR spectra indicated the presence of phenolic nuclei linked together by methylene groups in 0,0'-positions.
- PF 5 was used as the catalyst in place of the BF 3 .
- the product was a high melting solid.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyethers (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
This invention relates to novel aromatic compounds and to novel aromatic polymers of the compounds. The compounds of the present invention are cyclic ethers of orthobisphenol having the following structure: ##STR1## wherein R is independently selected from the group of hydrogen, chlorine, bromine or fluorine. The compounds of the present invention may be easily polymerized and the polymers exhibit good stability at high temperatures. The polymers are useful as molding compounds in applications where phenol-aldehyde and phenol-ketone condensates are now used.
Description
This is a continuation of application Ser. No. 570,545, filed Apr. 22, 1975, which is a continuation-in-part of Ser. No. 450,945, filed Mar. 13, 1974, both now abanonded.
The present invention relates to new cyclic ethers or ortho bisphenol and are produced by reacting a molar excess of orthobisphenol with bifunctional alkylene or alkylidene compound. It would be expected that such reaction would yield polymeric ethers, however, the products of the reaction are found to be a simple monomeric cyclic ether. The process is a condensation process and is carried out using an alkali metal or alkali metal hydroxide as a reactant, for example, sodium, potassium, or their hydroxide. The amount of alkali metal hydroxide used is generally between about 180 and 240 mole percent of the bisphenol utilized. Although additional amounts of alkali metal hydroxide may be used, the reaction is not proportionally speeded and additional subsequent removal problems will be encountered. The use of less than about 180% alkali metal hydroxide is operative, at a slower rate, however, the present process is not a rapid one and slowing the reaction does not appear to be advantageous.
The ethers of the present invention may be characterized by the following formula: ##STR2## wherein R is independently selected from the group of hydrogen, chlorine, bromine and fluorine.
The bifunctional alkylene or alkylidene compound utilized as a reactant, is suitably a dihalogen derivative such as dibromomethane or dichloromethane.
The reaction is effected by the formation of the corresponding alkali metal halide together with the ether product. The reaction may conveniently be carried out at atmospheric pressure and reflux temperatures. Under these conditions the time required for the reaction to go to completion varies with the reactants and their concentration, but may be as long as eight days. Such reaction may be illustrated: ##STR3##
Although the compounds per se, are useful in molding compounds, and in the preparation of polymers, particularly polymers which require high temperature stability, the halogenated compounds of the present invention have the added attribute of fire-retardant properties and are also useful as fire-retardant additives in plastic compositions. Further, the cyclic methyl ether of hexachlorophene: ##STR4## is found to have strong bactericidal power, similar to hexachlorophene. The methylene ether is soluble in various liquids which are poor solvents for hexachlorophene and are useful in the preparation of new bactericidal mixtures.
The cyclic ethers of the present invention may be easily polymerized using known techniques by reaction in the presence of a polymerization catalyst if either the R in the ortho or para positions of the phenol groups is hydrogen. Preferably, the R in the ortho position is hydrogen. Catalysts found most effective are BF3, BCl3 and PF5. A catalyst range of from 0.5 to 25% by weight of the methylene ether has been found useful. Suitably the polymerization reaction is carried out in an inert solvent such as hexane. The ether is initially mixed with the solvent, air removed, and the catalyst added. The reaction is suitably carried out at ambient temperature and pressure. The polymer products of the present invention may be characterized by the following formula: ##STR5## wherein R is independently selected from the group consisting of hydrogen, chlorine, bromine and fluorine and n is at least 5 and averages between about 30 and about 300.
The following examples, while not limiting, will illustrate various aspects of the invention. Unless otherwise specified, temperatures are given in degrees centigrade and parts are by weight.
Into a stirred reactor there was placed 100 parts of 0,0'-bisphenol F and 500 parts of ethylene glycol dimethylether. After heating to 85° C, 20 parts of sodium, which had been cut into small pieces, was slowly added. After all the sodium had reacted, 44 parts of CH2 Br2 was slowly added and the mixture was heated at 85° C for 18 hours. The reaction mixture was then poured into 2000 parts of water. The resulting solids were filtered and dried. They amounted to 40 parts and melted at 105°-107° C. The reacted bisphenol was recovered from the aqueous phase by acidification and extraction with ether.
The crude product was recrystallized from a 50/50 mixture of ethanol and water. It melted at 107°-109° C and had the following analysis: C 79.28%; H 5.11%; MW 214; calculated for the cyclic methylene ether: C 79.2%; H 5.7%; MW 212. The NMR and IR spectra showed that the cyclic structure had been formed.
Into a stirred reactor there was placed 50 parts of 0,0'-bisphenol F, 200 parts of 10% aqueous NaOH and 87 parts of CH2 Br2. This mixture was heated to reflux (90° C) and reacted for 20 hours. An additional 8 parts of CH2 Br2 was added and heating was continued for 20 more hours. The cooled reaction mixture was then poured into 2000 parts of water. The insoluble material was taken up in ether and the resulting solution washed with 5% aqueous NaOH until all unreacted bisphenol was removed. Evaporation of the solvent gave 42 parts of product that melted at 105-107. This was further purified by distillation (b.p. 112°-114° C/0.1 mm) and crystallization from 50/50 ethanol water. The final product melted at 109°-111° C.
A solution of 1007 parts of hexachlorophene in 10000 parts of ethylene glycol dimethyl ether was placed in the stirred reactor. This was heated to 80° C and 113 parts of sodium which had been cut into small pieces was slowly added. After the sodium had reacted, 435 parts of CH2 Br2 was added dropwise. The reaction was then held at 80° C for eight days. After cooling, the reaction mixture was poured into water and the resulting solids were taken up in hexane. The produce was separated from less soluble material by fractional crystallization. It was further purified by crystallization from a 75/25 mixture of hexane and ethylene glycol dimethyl ether and melted at 215°-219° C. A MW of 447 was found; theory, 419. Infrared spectra showed the absence of a band due to OH and the presence of an ether group, thus proving the cyclic ether structure.
A solution of 15 parts of the product of Example 2 in 1050 parts of hexane was placed in a small vessel. This was then evacuated, with some solvent flashing off, to remove air. Approximately 2 parts of BF3 was then introduced. Polymer slowly precipitated from solution. After 16 hours, the solvent was decanted and the polymer was washed with a dilute NaHCO3 solution. It was a high melting solid. Its infrared and NMR spectra indicated the presence of phenolic nuclei linked together by methylene groups.
The BF3 of Example 5 was replaced by BCl3. Polymer was recovered by evaporation of the solvent. Its infrared and NMR spectra indicated the presence of phenolic nuclei linked together by methylene groups in 0,0'-positions.
PF5 was used as the catalyst in place of the BF3. The product was a high melting solid.
While the present invention has been described with reference to certain specific embodiments, it will be recognized by those skilled in the art that many variations are possible without departing from the spirit and scope of the invention.
Claims (3)
1. The method of preparing a polymer by reaction of the monomer ##STR6## in the presence of a polymerization catalyst selected from the group consisting of BF3, BCl3 or PF5 to form ##STR7## wherein R in both formulas is independently selected from the group of hydrogen, chlorine, bromine and fluorine and n is at least 5.
2. The method of claim 1 wherein the catalyst range is from about 0.5 to about 25.0 percent by weight of the monomer.
3. The method of claim 1 wherein the reaction is carried out in an inert solvent comprising hexane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/711,651 US4051189A (en) | 1975-04-22 | 1976-08-04 | Cyclic ethers of phenolic compounds and polymers thereof |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US57054575A | 1975-04-22 | 1975-04-22 | |
| US05/711,651 US4051189A (en) | 1975-04-22 | 1976-08-04 | Cyclic ethers of phenolic compounds and polymers thereof |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US57054575A Continuation | 1975-04-22 | 1975-04-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US4051189A true US4051189A (en) | 1977-09-27 |
Family
ID=27075343
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US05/711,651 Expired - Lifetime US4051189A (en) | 1975-04-22 | 1976-08-04 | Cyclic ethers of phenolic compounds and polymers thereof |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US4051189A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4196250A (en) * | 1979-02-16 | 1980-04-01 | E. R. Squibb & Sons, Inc. | Polyether derivatives |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2499367A (en) * | 1947-03-07 | 1950-03-07 | Petrolite Corp | Chemical manufacture |
| US2499370A (en) * | 1947-03-07 | 1950-03-07 | Petrolite Corp | Process for breaking petroleum emulsions |
| US2730551A (en) * | 1952-03-24 | 1956-01-10 | Monsanto Chemicals | Halogenated tris-phenols |
| US2905737A (en) * | 1955-07-05 | 1959-09-22 | Firestone Tire & Rubber Co | Sulfur vulcanized rubber composition containing phenol reaction product as an oxidation inhibitor, and method of making same |
| US3151096A (en) * | 1959-06-03 | 1964-09-29 | Catalin Corp Of America | Halophenol derivatives as vulcanizing agents for butyl rubber and process of vulcanization |
| US3244671A (en) * | 1963-05-13 | 1966-04-05 | Hooker Chemical Corp | Production of phenolic novolac resins |
| US3378518A (en) * | 1959-09-28 | 1968-04-16 | Shell Oil Co | Polypropylene stabilizer with durylene bis-phenols |
| US3409571A (en) * | 1964-11-30 | 1968-11-05 | Hooker Chemical Corp | Phenol-aldehyde/phenol-ketone condensate-phosphorus containing esters |
| US3697459A (en) * | 1970-03-20 | 1972-10-10 | Hooker Chemical Corp | Aromatic polymers containing an element of the phosphorus family |
| US3737465A (en) * | 1969-12-16 | 1973-06-05 | Standard Oil Co | Bis-methylol compounds |
| US3876620A (en) * | 1973-04-26 | 1975-04-08 | Celotex Corp | Process of preparing phenolic-aldehyde polymer using o-cresol |
-
1976
- 1976-08-04 US US05/711,651 patent/US4051189A/en not_active Expired - Lifetime
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2499367A (en) * | 1947-03-07 | 1950-03-07 | Petrolite Corp | Chemical manufacture |
| US2499370A (en) * | 1947-03-07 | 1950-03-07 | Petrolite Corp | Process for breaking petroleum emulsions |
| US2730551A (en) * | 1952-03-24 | 1956-01-10 | Monsanto Chemicals | Halogenated tris-phenols |
| US2905737A (en) * | 1955-07-05 | 1959-09-22 | Firestone Tire & Rubber Co | Sulfur vulcanized rubber composition containing phenol reaction product as an oxidation inhibitor, and method of making same |
| US3151096A (en) * | 1959-06-03 | 1964-09-29 | Catalin Corp Of America | Halophenol derivatives as vulcanizing agents for butyl rubber and process of vulcanization |
| US3378518A (en) * | 1959-09-28 | 1968-04-16 | Shell Oil Co | Polypropylene stabilizer with durylene bis-phenols |
| US3244671A (en) * | 1963-05-13 | 1966-04-05 | Hooker Chemical Corp | Production of phenolic novolac resins |
| US3409571A (en) * | 1964-11-30 | 1968-11-05 | Hooker Chemical Corp | Phenol-aldehyde/phenol-ketone condensate-phosphorus containing esters |
| US3737465A (en) * | 1969-12-16 | 1973-06-05 | Standard Oil Co | Bis-methylol compounds |
| US3697459A (en) * | 1970-03-20 | 1972-10-10 | Hooker Chemical Corp | Aromatic polymers containing an element of the phosphorus family |
| US3876620A (en) * | 1973-04-26 | 1975-04-08 | Celotex Corp | Process of preparing phenolic-aldehyde polymer using o-cresol |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4196250A (en) * | 1979-02-16 | 1980-04-01 | E. R. Squibb & Sons, Inc. | Polyether derivatives |
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